WO2012118741A1 - Weatherable & abrasion resistant coating systems for polymeric substrates - Google Patents
Weatherable & abrasion resistant coating systems for polymeric substrates Download PDFInfo
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- WO2012118741A1 WO2012118741A1 PCT/US2012/026750 US2012026750W WO2012118741A1 WO 2012118741 A1 WO2012118741 A1 WO 2012118741A1 US 2012026750 W US2012026750 W US 2012026750W WO 2012118741 A1 WO2012118741 A1 WO 2012118741A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08J7/04—Coating
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/06—Polyurethanes from polyesters
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
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- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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Definitions
- the present invention relates to weatherable and abrasion resistant coating systems for polymeric substrates.
- Polymeric materials such as polycarbonate
- polycarbonate are promising alternatives to glass for use as structural material in a variety of applications, including automotive, transportation and architectural glazing applications, where increased design freedom, weight savings, and improved safety features are in high demand.
- Plain polycarbonate substrates are limited by their lack of abrasion, chemical, UV and weather resistance, and therefore need to be protected with optically transparent coatings that alleviate above limitations in the aforementioned applications.
- polycarbonate substrates are in general coated with thermally curable silicone hardcoat.
- thermally curable silicone hardcoat The poor weatherability of polycarbonate, on the other hand, is addressed with addition of organic or inorganic UV- absorbing materials in the silicone hardcoat layer.
- incorporation of UV absorbers, especially organic based, in the thermal curable silicone layer often leads to inferior abrasion resistance performance.
- One approach to address the limited abrasion resistance performance associated with the use of organic UV-absorbing materials is to use inorganic UV-absorbing materials at least partially in lieu of organic absorbing materials.
- the expected benefit is to avoid the addition of large amount of organics in the silicone hardcoat, thereby keeping abrasion resistance characteristics intact.
- the use of inorganic UV-absorbing materials can potentially help to achieve weatherability for extended period of time.
- inorganic UV-absorbing materials in the form of colloidal dispersion into an organic based coating composition, either with or without the presence of colloidal silica in the coating composition.
- the challenges relate to the ability to obtain long-term stable inorganic UV absorber dispersions, the ability to inhibit the agglomeration of colloidal particles of the inorganic UV absorbers, and the ability to maximize the loading of inorganic UV absorbers in order to maintain abrasion resistance characteristics without adversely affecting the film uniformity.
- Another approach to address the limited abrasion resistance of thermal curable silicone hardcoat is to deposit an abrasion resistant coating such as a hydrogenated silicon oxycarbide layer on top of commercially available thermally cured hardcoat systems by plasma techniques.
- an abrasion resistant coating such as a hydrogenated silicon oxycarbide layer
- the hydrogenated silicon oxycarbide layer-containing system is still not able to meet the 10-15 year durability requirements that the market demands.
- such a coating system is a relatively complex multilayer structure that is difficult to manufacture. Due to the costs of the raw material and the costs of processing and integration of multiple layers, the polycarbonate substrate coated with a hydrogenated silicon oxycarbide comprising system can be much more expensive than conventional glass.
- a primer composition comprising (1) an inorganic UV absorbing agent; and (2) a polymer selected from (i) a copo!ycarbonate comprising repeating units A and B, and (ii) a polyurethane obtained by reaction of a po!yisocyanate and a copolycarbonate diol comprising repeating units A and B,
- repeating units A and B are represented by the following formulae:
- moiar ratio of units (A) to units (B) is in the range of from about 9: 1 to about 1 :9, and wherein Ri is a divalent C8 to C12 aiicyclic group, R 2 is a divalent group selected from the group consisting of ethylene and propylene, n is an integer ranging from 4 to 40.
- the inorganic absorbing agent is selected from the group consisting of CeOx, TiOx, ZnOx, ZrOx, and combinations thereof, wherein x is 1-2.
- the primer composition is effective in holding a significant amount, on the order of 1 to 80% by weight based on the total weight of the primer composition, of inorganic absorbing agents. It is also suitable for promoting the adhesion between a substrate and an abrasion layer such as a thermal/UV cured organic-based topcoat or a hydrogenated silicon oxycarbide layer.
- a coated article including a polymeric substrate, a primer layer disposed on at least one surface of the substrate, and an abrasion-resistant layer disposed on the primer layer, wherein the primer layer is made from the primer composition specified above.
- the abrasion-resistant layer can be an organic-based topcoat or a hydrogenated silicon oxycarbide coating.
- a method for providing a polymeric substrate with a weather and abrasion-resistant coating system includes the steps of: (i) applying the primer composition of the invention onto a polymeric substrate; (ii) curing the primer composition to provide a primer layer; (iii) disposing an abrasion-resistant layer onto the primer layer thereby making a polymeric substrate with a weather and abrasion-resistant coating.
- Fig. 1 is a diagrammatic illustration of a coated article according to one embodiment of the invention.
- FIG. 2 is a diagrammatic illustration of a coated article according to another embodiment of the invention.
- FIG. 3 shows cross-section TEM analysis of an article coated according to the present invention.
- Fig. 4 illustrates the expected weatherability performance of a coated substrate according to the invention as compared to the weatherability performance of a substrate coated with Ce02-containing silicone hardcoat and a substrate coated with AS4000/SHP470 coating system.
- a primer composition suitable for providing adhesion of an abrasion-resistant layer to a substrate.
- the abrasion- resistant layer can be a thermal/UV cured organic-based topcoat or a hydrogenated silicon oxycarbide layer.
- the primer composition of the invention contains ( 1) at least one inorganic absorbing agent, and (2) a polymer selected from (i) a copolycarbonate, and (ii) a polyurethane derived from a copolycarbonate diol.
- the polymer severs as a matrix to hold the inorganic absorbing agent.
- the inorganic absorbing agent is not particularly limited. Suitable examples include, but are not limited to, CeOx, TiOx, ZnOx, ZrOx and mixture of these metal oxides, where x is 1 -2. In one embodiment, the inorganic absorbing agent is Ce0 2 .
- the polymer suitable for the primer composition of the invention can be either (i) a copolycarbonate comprising repeating units A and B, or (ii) a polyurethane obtained by reaction of a polyisocyanate and a copolycarbonate diol comprising repeating units A and B, wherein repeating units A and B are represented by the following formulae:
- is a divalent C8 to C 12 alicyciic group
- R 2 is a divalent group selected from the group consisting of ethylene and propylene
- n is an integer ranging from 4 to 40.
- repeating units (A) and (B) are present at a molar ratio ranging from about 1 :9 to about 9: 1 , preferably, from about 1 :3 to about 3: 1 , more preferably at a ratio of about 1 : 1.
- an alicyciic group is a non-aromatic group or unit.
- an alicyciic group is a non-aromatic carbocyclic or heterocyclic group and represents for example ring systems having from 6 to 10 carbon atoms.
- in repeating unit A is
- the molecular weight of the copolycarbonate is from about 500 to about 10 , preferably from about 1 to about 2 with respect to polystyrene standard.
- the alicyclic portion of the copolycarbonate brings in good film forming properties and the polyether portion helps to achieve aqueous/alcohol solubility.
- the oligomeric nature of these copolycarbonates (Mn ⁇ 1 - 2 K) also favors both film forming and solubility requirements for primer compositions.
- the copolycarbonate of the invention contains terminal groups.
- Each terminal group is a member selected from the group consisting of a hydroxy! group, and a substituted silyl group of the formula:
- R 1 is a monovalent hydrocarbon residue having 1 to 10 carbon atoms, preferably, from 1 to 3 carbon atoms
- each Y is independently a member selected from the group consisting of a halogen atom, an alkoxy group having 1 to 10 carbon atoms, preferably from 1 to 3 carbon atoms, and an acyloxy group having 1 to 10 carbon atoms, preferably from 1 to 3 carbon atoms
- a is a number having a value of from 1 to 3.
- a is 3 and Y is an alkoxy group, preferably a methoxy or a ethoxy group.
- copolycarbonate having hydroxyl groups at its terminals are diols and representative examples of such copolycarbonate diols are represented by the formula:
- Ri, R 2 and n are as defined above, and wherein x and y are chosen in such a way that the molar ratio of x : y is between from about 1 :9 to about 9: 1 and the molecular weight of the copolycarbonate diol is from about 500 to about ! O , preferably from about 1 to about 2K with respect to polystyrene standard.
- the copolycarbonate diols of the invention can be prepared by the condensation reaction of an alicyclic diol and a polyether with ethylene carbonate as the carbonate source, or other methods that are known to those skilled in the art.
- Suitable alicyclic diols include, but are not limited to, cyclohexanedimethanol (CHDM) and tricyclodecanedimethanol (TCDDM).
- Suitable polyethers include polypropylene glycol (PPG) and polyethylene glycol (PEG).
- PPG polypropylene glycol
- PEG polyethylene glycol
- the polyether has a molecular weight of from about 300 to about 3000.
- the copoiycarbonate diols of the invention can be further silylated, either fully or partially.
- Silylation of the hydroxyl-termiiiated copolycarbonates can be accomplished by reacting the copoiycarbonate diol with an isocyanatosilane. Suitable isocyanatosilanes are those of the genera! formula:
- R 3 is a divalent alkylene group of from 1 to 10, preferably from 1 to 3 carbon atoms
- R 1 is a monovalent hydrocarbon residue having 1 to 10, preferably from 1 to 3 carbon atoms
- each Y is independently a member selected from the group consisting of a halogen atom, an alkoxy group having 1 to 10, preferably 1 to 3 carbon atoms, an acyloxy group having 1 to 10, preferably 1 to 3 carbon atoms
- a is a number having a value of from 1 to 3.
- a is 3 and Y is an alkoxy group, preferably a methoxy or a ethoxy group.
- R 3 is a divalent propyl group.
- Examples of such isocyanatosilane for use in the silylation procedure are a- isocyanatomethyltrimethoxysilane, ⁇ -isocyanatoethyltrimethoxysilane, ⁇ - isocyanatopropyltrimethoxysilane, a-isocyanatomethyltriethoxysilane, ⁇ - isocyanatoethyltriethoxysilane, and ⁇ -isocyanatopropyltriethoxysilane.
- the silylation of the hydroxyl-te minated copolycarbonates herein can be substantially complete, i.e., essentially no hydroxyl groups will be present following silylation.
- silylation will be incomplete, or partial.
- levels of silylation of not more than about 95 molar percent, and advantageously, not more than 90 molar percent, of the total hydroxyl groups present in the copolycarbonate is generally suitable and can be achieved by appropriate adjustment of the amounts of isocyanatosilane being reacted for a given hydroxyl-terminated copolycarbonate.
- the polyurethanes suitable for use in the primer composition of the invention are derived from the reaction of at least one copolycarbonate diol as specified above in the context of one embodiment of polymer (i) with at least one polyisocyanate.
- the isocyanates used to prepare polyurethanes of the invention are organic isocyanates and include any of the known and conventional organic polyisocyanates, especially organic diisocyaiiates.
- the polyisocyanate is a diisocyanate represented b the formula OCN-R4-NCO, wherein R 4 is selected from
- the polyurethane suitable for use in the primer composition of the invention may be prepared by mixing the hydroxy-terminated polymer and organic isocyanate together at ambient temperature and pressure, although the rate of the reaction is significantly increased if the temperature of the reaction mixture is raised to a higher temperature, for example, a temperature between 60-100°C and / or in the presence of organo-nietallic catalysts such as tin based catalysts (dibutyitin dilaurate (DBTDL)).
- DBTDL dibutyitin dilaurate
- the polyurethane may be hydroxyl-terminated or isocyanate-terminated.
- a molar ratio of NCO to OH from about 1. 1 to about 4.0, depending on the selection of the particular copoiycarbonate diol, is used to provide isocyanate-terminated polyurethane prepolyiners.
- a molar ratio of NCO to OH from about 0.3 to about 0.95, and more preferably from about 0.5 to about 0.9, depending on the specific copoiycarbonate diol, is used to provide hydroxyl group-terminated polyurethane prepolymers.
- the polyurethane is hydroxy- terminated.
- Silylation of the isocyanate-terminated polyurethane described herein can be accomplished by reacting the polyurethane with a silane possessing at least one hydrolyzable group and at least one functionality which is reactive for isocyanate, i.e., an active hydrogen- containing group such as hydroxyl, carboxylic acid, mercapto, primary amino or secondary amino.
- a silane possessing at least one hydrolyzable group and at least one functionality which is reactive for isocyanate i.e., an active hydrogen- containing group such as hydroxyl, carboxylic acid, mercapto, primary amino or secondary amino.
- the silane is a primary or secondary aminosilane of the general formula:
- s is hydrogen or an alkyl group of from 1 to 10 carbon atoms
- R 7 is a divalent alkylene group of from 1 to 10 carbon atoms
- R 2 and R 3 each independently is an alkyl group of from 1 to 6 carbon atoms or an aryl group of from 6 to 8 carbon atoms
- b has a value of 0, 1 or 2.
- R 7 is a divalent alkylene group of 1 to 3 carbon atoms
- R 3 is an alkyl group of from 1 to 3 carbon atoms.
- aminosilanes for use in the silylation procedure herein are 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-amino-3,3- dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyidimethoxymethylsilane, N- methyl-3-amino-2-methylpropylirimethoxysilane, N-ethyl-3-amino-2- methylpiOpyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyldiethoxymethylsilane, N- ethyl-3-ammo-2-methyfpi pyltriethoxy si!ane, N-ethyl-3-amino-2- methylpropyimethyldimethoxysilane, N-biityl-3-amino-2-methylpropyitrimethoxys
- Silylation of the hydroxyl-terminated polyiirethane described herein can be accomplished by reacting the polyiirethane with an isocyanatosilane.
- Suitable isocyanatosilanes are those of the general formula:
- R 8 is a divalent alkylene group of from 1 to 10, preferably 1 to 5 carbon atoms
- R 1 * and R 5 each independently is an alkyl group of from 1 to 6 carbon atoms or an aryl group of from 6 to 8 carbon atoms
- c has a value of 0, 1 or 2.
- c is zero
- R 5 is a C 1 -C5, preferably C I to C3 alky! group
- R 8 is a divalent alkylene group having from 1 to 3 carbon atoms.
- the silylation of the hydroxy-term inated or isocyanate-terminated polyiirethane prepolymers herein can be partially or substantially complete, i.e., essentially no hydroxyl and/or isocyanate groups will be present following silylation.
- the primer composition of the invention includes a solvent.
- the solvent is not particularly limited.
- Exemplary solvent includes alcohols, such as methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, methoxypropanol, ethylene glycol, diethylene glycol butyl ether, or combinations thereof.
- Other water miscible organic solvents such as acetone, methyl ethyl ketone, ethylene glycol monop opyl ether, and 2-biitoxy ethanol, can also be utilized.
- the primer composition of the invention can also include other additives such as hindered amine light stabilizers, antioxidants, dyes, flow modifiers, and leveling agents.
- Polyether-polysiloxane copolymers such as BYK®TM-33 1 manufactured by BY ®-Chemie are commonly added as a flow modifier/leveling agent.
- the primer composition of this invention can be prepared by simply mixing the inorganic UV-absorbing agent and the polycarbonate copolymer (i) or polyurethane polymer (ii) and the optional ingredients in a solvent.
- the order of mixing of the components is not critical. The mixing can be achieved through any means known to a person skilled in the art, for example, milling, blending, stirring, and the like.
- the primer compositions with varying loading of inorganic UV absorbing agents such as Ce0 2 are found to be stable for several months or greater than 1 year.
- the primer compositions of the invention can be suitably coated onto a polymeric substrate such as a plastic surface.
- plastics include synthetic organic polymeric materials, such as acrylic polymers, for example, poiy(methylmethacrylate), and the like; polyesters, for example, poly(ethylene terephthalate), poiy(butylene terephthalate), and the like; polyamides, polyimides, acryionitrile-styrene copolymer, styrene-acrylonitrile- butadiene terpolymers, polyvinyl chloride, polyethylene, and the like, polycarbonates, and copolycarbonates such as EXL, high-heat polycarbonates.
- the preferred substrate is formed of polycarbonate or an acrylic resin.
- Polycarbonates are especially preferred materials for transparent substrates because of their excellent physical, mechanical and chemical properties. In general, the choice of substrate is ultimately determined by the contemplated end use.
- the primer composition of the invention is coated on a substrate by flow coat, dip coat, spin coat or any other methods known to a person skilled in the field, it is allowed to dry by removal of any solvents, for example by evaporation, thereby leaving a dry coating.
- the primer composition can subsequently be cured to provide a primer layer.
- the primer layer with inorganic absorbing agents such as metal oxide nanoparticles (specifically Ce0 2 ) loading of 1 - 80 wt % in dry film can be made, It is believed that other types of metal oxide nanoparticles can be made at a loading of 1 - 80 wt% in dry film as well.
- the primer layer formed from the primer composition of the invention is effective in providing adhesion of an abrasion layer to a substrate and can be used as part of a coated article of the invention.
- a coated article including a polymeric substrate, a primer layer disposed on at least one surface of said substrate, and an abrasion-resistant layer disposed on said primer layer, wherein said primer layer is made from any of the primer composition of the invention disclosed herein.
- Figures 1 and 2 depict illustrative, non-limiting examples of coated articles according to different embodiments of the invention.
- coated article 1 includes substrate 2, primer layer 3 disposed on a surface of substrate 2, and organic-based topcoat 4 disposed on primer layer 3.
- the topcoat is formed by first applying a coating composition onto the primer layer, followed by curing the composition.
- the topcoat composition is not particularly limited. Silicone hardcoats comprised of a siloxanoi resin/colloidal silica dispersions are one example of a coating composition that may be used as a topcoat.
- the topcoat may contain additional organic UV-absorbing agents if desired, but the loading can be lower than those that do not have inorganic absorbing agent in either the primer layer or the hardcoat layer. Thus the abrasion integrity is maintained and in some cases improved by limiting the amount of organic UV-absorbing agent, while at the same time, the weatherability is improved.
- Siloxanoi resin / colloidal silica dispersions are known in the art. Generally, these compositions have a dispersion of colloidal silica in an aliphatic alcohol/water solution of the partial condensate of an alkyltrialkoxysilane, which can be methyltrimethoxysilane. Aqueous colloidal silica dispersions generally have a particle size in the range of 5 to 150 millimicrons in diameter. These silica dispersions are prepared by methods well-known in the art and are commercially available. Depending upon the percent solids desired in the final coating composition, additional alcohol, water, or a water-miscible solvent can be added.
- the solvent system should contain from about 20 to about 75 weight percent alcohol to ensure solubility of the siloxanoi formed by the condensation of the silanol.
- a minor amount of an additional water-miscibie polar solvent such as acetone, butyl ceilosolve, and the like can be added to the water-alcohol solvent system.
- the composition is allowed to age for a short period of time to ensure formation of the partial condensate of the silanol, i.e., the siloxanol.
- Examples of aqueous/organic solvent borne siioxanol resin / colloidal silica dispersions can be found in U.S. Pat. No.
- U.S. Pat. No. 4, 177,315 to Ubersax discloses a coating composition comprising from about 5 to 50 weight percent solids comprising from about 10 to 70 weight percent silica and about 90 to 30 weight percent of a partially polymerized organic silanol of the general formula RSi(OH) 3 , wherein R is selected from methyl and up to about 40% of a radical selected from the group consisting of vinyl, phenyl, gamma- glycidoxypropyl, and gamma-niethacry!oxypropyl, and about from 95 to 50 weight percent solvent, the solvent comprising about from 10 to 90 weight percent water and about from 90 to 10 weight percent lower aliphatic alcohol, the coating composition having a pH of greater than about 6.2 and less than about 6.5.
- U.S. Patent No. 4,476,281 to Vaughn describes hardcoat composition having a pH from 7.1 -7.8.
- U.S. Pat. No. 4,239,798 to Olson et al. discloses a thermoset, siiica-filled, oiganopolysiloxane top coat, which is the condensation product of a silanol of the formula RSi ⁇ OH) 3 in which R is selected from the group consisting of alkyl radicals of 1 to 3 carbon atoms, the vinyl radical, the 3,3,3- trifluoiOpropyl radical, the gamma-glycidoxypropyl radical and the gainma- methacryloxypropyl radical, at least 70 weight percent of the silanol being CH 3 Si(OH) 3 .
- the content of the foregoing patents are herein incorporated by reference.
- the siloxanol resin / colloidal silica dispersions described herein above can contain partial condensates of both organotrialkoxysilanes and diorganodialkoxysilanes; and can be prepared with suitable organic solvents, such as, for example, 1 to 4 carbon alkanol, such as methanol, ethanol, propanol, isopropanol, butanol; glycols and glycol ethers, such as propyleneglycolmethyl ether and the like and mixtures thereof.
- suitable organic solvents such as, for example, 1 to 4 carbon alkanol, such as methanol, ethanol, propanol, isopropanol, butanol
- glycols and glycol ethers such as propyleneglycolmethyl ether and the like and mixtures thereof.
- UV absorbers can be employed at levels from about 2 to about 20 weight percent of the total composition. Suitable UV absorbers are those which co-react with partial hydolyzate and are less likely to volatilize during the heat cure. Exemplary UV absorbers include 4[gamma-(trimethoxysilyl)propoxy]-2-hydiOxybenzophenone, 4[gamma- (triethoxysilyl)propoxy]-2-hydroxybenzophenone, 2- [(tnethoxysilyljpropyljdibenzylresorcinol, hydroxy benzophenone and benzotriazole serves as wel! as the triazine, cyanoacrylates and benzylidene malonates or their mixtures.
- additives such as hindered amine light stabilizers, antioxidants, dyes, flow modifiers and leveling agents or surface lubricants can be used.
- Other colloidal metal oxides can be present at up to about 10% by weight of the aqueous/organic solvent borne siloxanol resin / colloidal silica dispersion and can include metal oxides such as, antimony oxide, cerium oxide, aluminum oxide, zinc oxide, and titanium dioxide.
- the commercial coating products AS4000TM, AS4700TM, SHC2050TM (Momentive Performance Materials), SILVUETM 121 , SILVUETM 339, SILVUETM MP 100 (SDC Technologies), and Hi-GARDTM 1080 (PPG) are all examples of coatings based on siloxanol resin / colloidal silica dispersions.
- coated article 5 includes a substrate 6, a primer layer 7 deposited on a surface of substrate 6, and a hydrogenated silicon oxycarbide layer 8 deposited on primer layer 7.
- the hydrogenated silicon oxycarbide layer can be deposited on the primer layer via physical vapor deposition or plasma deposition techniques. Exemplary techniques include but are not limited to plasma enhanced chemical vapor deposition, expanding thermal plasma, microwave plasma, inductively coupled plasma, and high density plasma chemical vapor deposition.
- the hydrogenated silicon oxycarbide layer may also be deposited onto the primer layer by one of sputtering, laser ablation, cathodic arc deposition, and electron beam evaporation.
- an organic-based topcoat can be deposited on the hydrogenated silicon oxycarbide layer to provide additional abrasion resistance and weatherability to the polymeric substrate.
- primer compositions 1 -4 with varying loading of CHDM-PPG coPC and cerium oxide were prepared and shown below in Tables 1 - 4. These compositions were found to be suitable to use as a primer, as a visually uniform layer was resulted when applied onto the polycarbonate substrate and dried. Similar results were observed when screened CHDM-PPG coPC with Mn ⁇ 2 .
- CHDM-PEG coPC was prepared and used in the primer composition.
- PEG stands for polyethylene glycol. Examnle 3 TCDDM-PPG coPC-CeO? based primer compositions
- TCDDM-PPG coPC was prepared and used in the primer composition.
- TCDDM stands for tricyclodecanedimethanol .
- TCDDM-PEG coPC was prepared and used in the primer composition
- Example 8 Mixture of silylated-CHDM-PPG coPC and silviatd-TCDDM-PPG coPC- CeOj based primer compositions
- PMMA poly(methylmethacryiate)
- diacetone alcohol in a round bottom flask was stirred at room temperature for 5 minutes. Subsequently, 1 -methoxy- 2-propanol was added while stirring at room temperature. To the above solution, aqueous cerium oxide (20wt%) was slowly added over a period of 5 minutes at room temperature. PMMA was precipitated as soon as aqueous CeC»2 was added. This shows that PMMA/Ce0 2 dispersion is not suitable to use as a primer composition.
- Primer composition 1 described in example 1 was coated onto a polycarbonate substrate. The solvent was subsequently evaporated; and the primer composition was cured to provide a primer layer.
- the silicone hardcoat assembly containing SHP470 as a primer and AS4700 as a topcoat was prepared to provide Comparative Coating Example A.
- the specific combinations of the primer and the topcoat for Coating Examples 1 and 2 and Comparative Coating Example A are given in table 7.
- Coating Example 2 for PC showed good abrasion resistance, adhesion and optical properties, similar to SHP470/AS4700 coat. Similar properties are observed for Coating Example 1 where the topcoat doesn't contain an organic UV absorber. As inferred from the cross-section TE analysis as shown in Figure 3, there are no micro- cracks and de!amination at the interfaces (PC/primer/top-coat).
- Coating Example 3 A mixture of 2.0 g of CHDM-PPG coPC (Mn ⁇ 1 .2 K), 24.00g diacetone alcohol, and 24.00g i -methoxy-2-piOpanol was mixed at room temperature to provide a solution. To the CHDM-PPG coPC solution was added 2.04g aqueous cerium oxide (20wt%). The resultant was stirred to make a homogeneous dispersion. To the dispersion was added 0.004g of BYK®-331 as a flow/leveling agent to provide a primer composition. The primer composition was a yellow clear liquid (pH 3.5 - 4.4).
- This primer composition was coated onto a polycarbonate substrate. The solvent was removed and the primer composition was cured to provide a primer layer. The silicone topcoat as described in example 1 i , part A was coated onto the primer layer and thermally cured to provide Coating Example 3.
- Comparative Coating Example B To the silicone liardcoat prepared in Part A of Example 1 1 was added CeC> 2 to provide a CeCh-containing liardcoat. The CeCVcontaining liardcoat was coated onto an unprimed glass substrate to provide Comparative Coating Example B.
- Comparative Coating Example C A polycarbonate substrate was primed with SHP470 and then coated with AS4000 as a topcoat to provide Comparative Coating Example C.
Abstract
Description
Claims
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KR20137024727A KR20140010084A (en) | 2011-02-28 | 2012-02-27 | Weatherable and abrasion resistant coating systems for polymeric substrates |
CN201280020748.7A CN103492502B (en) | 2011-02-28 | 2012-02-27 | Weather-proof and wear-resisting coat system for polymeric substrate |
BR112013021992A BR112013021992A2 (en) | 2011-02-28 | 2012-02-27 | abrasion and weather resistant coating systems for polymeric substrates |
JP2013556770A JP6026440B2 (en) | 2011-02-28 | 2012-02-27 | Weather and wear resistant coating systems for polymer substrates |
MX2013009823A MX352027B (en) | 2011-02-28 | 2012-02-27 | Weatherable & abrasion resistant coating systems for polymeric substrates. |
ES12716784.9T ES2591008T3 (en) | 2011-02-28 | 2012-02-27 | Weather and abrasion resistant coating systems for polymeric substrates |
EP12716784.9A EP2681285B1 (en) | 2011-02-28 | 2012-02-27 | Weatherable and abrasion resistant coating systems for polymeric substrates |
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JP2014511421A (en) | 2014-05-15 |
US20120219803A1 (en) | 2012-08-30 |
BR112013021992A2 (en) | 2016-11-16 |
KR20140010084A (en) | 2014-01-23 |
US8940397B2 (en) | 2015-01-27 |
MX2013009823A (en) | 2014-01-08 |
MX352027B (en) | 2017-11-07 |
ES2591008T3 (en) | 2016-11-24 |
TW201239048A (en) | 2012-10-01 |
CN103492502A (en) | 2014-01-01 |
CN103492502B (en) | 2016-08-24 |
EP2681285B1 (en) | 2016-07-13 |
TWI530540B (en) | 2016-04-21 |
EP2681285A1 (en) | 2014-01-08 |
JP6026440B2 (en) | 2016-11-16 |
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